Alkyl phenol-sulfur condensates as fuel and lubricating oil additives

ABSTRACT

Additives for improving the low temperature flow properties and oxidative stability of hydrocarbon oils are disclosed, which comprise the condensation reaction product of alkylated phenol and sulfurizing agent, wherein: 
     (a) the polymer composition has a number average molecular weight of at least about 3,000 and a molecular weight distribution of at least about 1.5; 
     (b) in the alkylated phenol reactant the alkyl groups (i) are essentially linear; (ii) have between 6 and 50 carbon atoms; and (iii) have an average number of carbon atoms between about 12 and 26; and 
     (c) not more than about 10 mole percent of the alkyl groups on the alkylated phenol have less than 12 carbon atoms and not more than about 10 mole percent of the alkyl groups on the alkylated phenol have more than 26 carbon atoms. The additives may also be produced in a branched backbone form in which monomer reactants are compolymerized with certain tri- or tetrafunctional comonomers. Blends of these additives with various hydrocarbon oils, and particularly various middle distillates and lubricating oil compositions, whose low temperature flow properties and oxidative stability are significantly improved thereby, are also disclosed.

This is a division of application Ser. No. 107,457, filed Oct. 8, 1987,now U.S. Pat. No. 4,976,882.

FIELD OF THE INVENTION

The present invention relates to multi-functional additives forimproving both the low temperature flow properties and the oxidationstability of hydrocarbon oils. More particularly, the present inventionrelates to additives for improving the low temperature flow propertiesand oxidation stability of fuel oil and lubricating oil compositions.Still more particularly, the present invention relates to fuel oil andlubricating oil compositions having both improved low temperature flowproperties and improved oxidation stability. Still more particularly,the present invention relates to methods for producing additives forimproving the low temperature flow properties and oxidation stability ofthese various hydrocarbon oil compositions.

BACKGROUND OF THE INVENTION

A large variety of additives for improving various properties inhydrocarbon oil compositions are well known, and in fact a large numberof these compositions are being used on a commercial level. The variousadditives are used for a variety of purposes, some of which relate toimproving the low temperature (i.e., less than about 30° F.) flowproperties of various types of hydrocarbon oils, including bothlubricating oil fractions and other oil fractions including heatingoils, diesel oils, middle distillates, and the like, and others of whichrelate to improving the oxidation stability of these various types ofhydrocarbon oils. These flow improvers generally modify the wax crystalsin both lubricating oils and other hydrocarbon fractions and crudes soas to impart low temperature handling, pumpability, and/or vehicleoperability thereto. These parameters are generally measured by avariety of tests, including pour point, cloud point, mini-rotaryviscometry (MRV) and others. Those other additives are used primarilyfor imparting anti-oxidant properties to these hydrocarbon fractions,including lubricating oil fractions.

Cloud point (ASTM D 2500) is the temperature at which wax crystals firstappear as a haze in a hydrocarbon oil upon cooling. Such wax crystalstypically have the highest molecular weight of the waxes in thehydrocarbon oil and therefore the lowest solubility. The cloud point ofa hydrocarbon oil reflects the temperature at which problems infiltering the oil are encountered. However, the cloud point of alubricating oil (as opposed to a fuel oil) is of less significance thanis its pour point because the filters typically encountered by alubricating oil (e.g., combustion engine oil filters) have a relativelylarge pore size, and filter plugging is therefore less of a problem inthese environments.

Pour point is the lowest temperature at which a hydrocarbon oil willpour or flow when chilled, without disturbance, under specifiedconditions. Pour point problems arise through the formation of solid orsemi-solid waxy particles in a hydrocarbon oil composition under chilledconditions. Thus, as the temperature of the oil is decreased, thedistribution of such oil by pumping or siphoning is rendered difficultor impossible when the temperature of this oil is around or below thepour point of the oil. Consequently, when the flow of oil cannot bemaintained, equipment can fail to operate.

It has therefore been necessary to develop various additives for thepurpose of influencing the cold temperature flow properties ofhydrocarbon oils.

The general term "lubricating oil flow improver" (LOFI) covers all thoseadditives which modify the size, number, and growth of wax crystals inlube oils in such a way as to impart improved low temperature handling,pumpability, and/or vehicle operability as measured by such tests aspour point, cloud point, and mini rotary viscometry (MRV). The majorityof lubricating oil flow improvers are polymers or contain polymers.These polymers are generally of two types, either backbone or sidechain.

The backbone variety, such as the ethylenevinyl acetates (EVA), havevarious lengths of methylene segments randomly distributed in thebackbone of the polymer, which associate or cocrystallize with the waxcrystals inhibiting further crystal growth due to branches andnon-crystallizable segments in the polymer.

The sidechain-type polymers, which are the predominant variety used asLOFI's, have methylene segments as the side chains, preferably asstraight side chains. These polymers work similarly to the backbone typeexcept the side chains have been found more effective in treatingisoparaffins as well as n-paraffins found in lube oils. Morespecifically, LOFI's are typically derived from unsaturated carboxylicacids or anhydrides which are esterified to provide pendent ester groupsderived from a mixture of alcohols. Most current commercial additives ofthis type thus require the use of relatively expensive alcohols fortheir production. Representative examples of this type of side chainLOFI include dialkyl fumarate/vinyl acetate copolymers and esterifiedstyrene/maleic anhydride copolymers.

It would be extremely advantageous if additives could be developed whichrely on less expensive olefins rather than alcohols in the synthesis oflow temperature flow improvers without sacrificing the properties ofconventional alcohol-based LOFI's. Several commercially unsuccessfulattempts have been made in the past using alkylated phenol formaldehydecondensates.

One additive composition which has been disclosed as a pour depressantfor fuels and crude oils is set forth in British Patent No. 1,173,975.The additive disclosed in this patent is a phenol-aldehyde (preferablyformaldehyde) polymer in which the phenol has an R-- or RCO--substituent in which R is hydrocarbyl or substituted hydrocarbyl. R isfurther said to contain from 18 to 30 carbon atoms, and is preferably astraight chain alkyl group. The specific examples in this patent whichuse olefins to provide these R groups include various internal olefins,and there is no specific disclosure regarding the advantages of usingterminal olefins therein. Another patent, British Patent No. 1,167,427,discloses the use of esters of such phenolaldehyde polymers for pourpoint reduction of fuel oils. In both of these British patents, the oilsto be treated are said to have a maximum viscosity of about 1500 cSt at100° F., and neither recognizes the significance of utilizing specificalpha-olefins and mixtures thereof to produce these condensationproducts, or the advantages of imparting essential linearity to theolefin derived side chains.

Another class of such additives are essentially known as anti-oxidantsor oxidation stabilizers. It is thus know that a number of phenolic andsulfur-containing compounds possess anti-oxidant properties inconnection with various organic materials which are subject to oxidativedecomposition in the presence of air, oxygen or ozone. These include,for example, U.S. Pat. No. 3,060,121. In this patent compounds have thegeneral formula ##STR1## in which R, in its broadest sense, containsfrom 1 to 22 carbon atoms, R₁ and R₂ are up to 3 carbon atoms, A₁ is upto 10 carbon atoms, x can be 3, and the maximum molecular weight underthese conditions would thus be 1,346. These compounds are disclosed asanti-oxidants for certain organic materials. However, the compoundsdisclosed in this patent have relatively low molecular weights, againgenerally not more than about 1,350 as set forth above.

U.S. Pat. No. 3,986,981 discloses yet another class of anti-oxidants inthis case comprising bisphenolic polymers in which the repeating unitscan include compounds of the formula ##STR2## in which the R₂₋₄ radicalscan comprise alkyl groups of from 1 to 8 carbon atoms, connected bysulfur methylene or butylidene bridging groups. Again, however, thecompounds in question are of relatively low molecular weights.

Similarly, U.S. Pat. No. 3,951,830 discloses lubricant additivesparticularly useful as oxidation inhibitors comprising sulfur andmethylene-bridged polyphenol compositions which are produced fromreacting phenol with formaldehyde and subsequently sulfurizing themethylene-bridge intermediate, or as an alternative sulfurizing thephenol and then reacting same with formaldehyde. The product of same isbelieved to be a sulfur and methylene-bridged polyphenol composition, inwhich the phenol can be substituted with aliphatic or cycloaliphaticradicals of at least 6 carbon atoms and up to as many as 7,000 carbonatoms. However, all the examples in this patent use branched olefinssuch as polyisobutylene substituted phenols therein.

U.S. Pat. No. 4,446,039 discloses yet another additive for fuels andlubricants which, in this case, is prepared by reacting aromaticcompounds, such as phenol or substituted phenol including alkyl groupsof at least 50 carbon atoms, with an aldehyde, such as formaldehyde, anda non-amino hydrogen, active hydrogen compound, such as phenol,optionally along with an aliphatic alkylating agent of at least 30carbon atoms. This patent also discloses that sulfurized additivecompositions thereof can also be used as lubricant additives and fueloil additives. It does not disclose the use of alpha-olefins of lessthan 50 carbon atoms for the alkylation of phenol.

Another additive for improving the various cold flow characteristics ofhydrocarbon fuel compositions is disclosed in U.S. Pat. No. 4,564,460.In this patent the additives are broadly disclosed as including eitheran oil soluble ethylene backbone polymer or varioushydrocarbyl-substituted phenols as a first component and variousreaction products of hydrocarbyl-substituted carboxylic acylating agentsand amines and/or alcohols. The hydrocarbyl-substituted phenolconstituents of this overall additive are also broadly described, andthey can include repeating aromatic moieties, such as those shown incolumn 14 thereof, in which the R* groups include substantiallysaturated monovalent hydrocarbon-based polymers of at least about 30aliphatic carbon atoms or hydrocarbyl groups of from 8 to 30 carbonatoms. These, in turn, can be provided by internal olefins oralphaolefins, and can be either straight or branched. Furthermore, atcolumn 14, lines 1-40 of the patent the phenol compounds are disclosedas including various bridging compounds, including --S-- (line 36).Notwithstanding the extremely broad disclosure of this patent, not asingle working example is provided therein which makes or tests anyhydrocarbyl substituted phenol or aldehyde condensation product thereof.

British Patent No. 2,062,672 discloses another such additive, in thiscase including a sulfurized alkyl phenol and a carboxylic dispersant.The alkyl phenols disclosed in this patent can include alkyl radicals ofup to 1000 carbon atoms, but the disclosure also mentions the use ofmethylene-bridged alkyl phenols prepared by the reaction of the alkylphenol and formaldehyde.

Canadian Patent No. 1,192,539 discloses yet anotheralkyl=phenol-containing lubricant additive. In this case the lubricantis designed for two-cycle engines and the phenolic compound includes ahydrocarbyl group of an average of at least ten aliphatic carbon atoms,and preferably containing at least 30 and up to 400 aliphatic carbonatoms (page 11, lines 13-17). Furthermore, the disclosure states thatthe aromatic ring can be a linked polynuclear aromatic moiety, which canalso include other substituents, and which can be linked by a number ofgroups, including sulfide linkages (page 6, lines 1-8). Once again inthis case the disclosure is very broad, and includes innumerablevariations on the alkyl phenol component.

There are also a number of patents which disclose other alkyl phenolpolysulfides, primarily disulfides, as additives to mineral oils toimprove properties including high temperature stability thereof. Theseinclude U.S. Pat. No. 2,174,248 which teaches the use of alkyl phenolsproduced from olefins of from 2 to 8 carbon atoms with the sulfurcompound to produce the disulfide. Also, U.S. Pat. Nos. 2,198,828 and2,209,463 have similar disclosures in this regard.

British Patent No. 2,062,672 discloses another such additive, in thiscase including a sulfurized alkyl phenol and a carboxylic dispersant.The alkyl phenols disclosed in this patent can include alkyl radicals ofup to 100 carbon atoms, but the disclosure also mentions the use ofmethylene-bridged or sulfur bridged alkyl phenols prepared by thereaction of the alkyl phenol and formaldehyde or a sulfurizing agent.

U.S. Pat. No. 3,629,225 also discloses sulfurized alkyl phenols oflimited size (up to three repeating units), and U.S. Pat. No. 4,305,832discloses a sulfurized phenol composition as set forth in column 1thereof in which the phenols include an alkyl group having from 1 to 18carbon atoms, and the overall compositions again have a limitedmolecular weight with up to four repeating units therein.

Irrespective of all of the above, and the large number of additivecompositions which have previously been proposed and utilized foraltering both the flow properties and the oxidative stability ofhydrocarbon oils and lubricating oil compositions, the search hascontinued for additional additive compositions which can improve boththe flow characteristics and the oxidative stability of these varioushydrocarbon compositions, and which can also be easily produced on aneconomical basis.

Commonly assigned U.S. patent application Ser. No. 107,507, filed onOct. 8, 1987 now U.S. Pat. No. 5,039,473 by the inventors herein isdirected to alkyl phenol-aldehyde condensates and sulfurized derivativesthereof, derived from the alkylated phenols described herein and usedfor the same purposes as described herein.

SUMMARY OF THE INVENTION

In one aspect of the present invention, there is provided a polymercomposition capable of improving both the low temperature flowproperties and the oxidation stability of hydrocarbon oils comprisingthe condensation reaction product of reactants comprising alkylatedphenol, comprising at least 80 mole percent of difunctional alkylatedphenol, and a sulfurizing agent wherein:

(a) the polymer composition has a number average molecular weight of atleast about 3,000 and a molecular weight distribution of at least about1.5;

(b) in the alkylated phenol reactant the alkyl groups (i) areessentially linear; (ii) have between 6 and 50 carbon atoms; and (iii)have an average number of carbon atoms between about 12 and 26; and

(c) not more than about 10 mole percent of the alkyl groups on thealkylated phenol have less than 12 carbon atoms and not more than about10 mole percent of the alkyl groups on the alkylated phenol have morethan 26 carbon atoms.

In a preferred embodiment, the polymeric composition can be representedby the formula: ##STR3## wherein (a) x comprises an integer from 1 toabout 8; (b) R₁ represents alkyl derived from linear alpha-olefinshaving from 6 to 50 carbon atoms; (c) R₂, R₃, R₄ and R₅ representhydrogen or alkyl derived from linear alpha-olefins having from 6 to 50carbon atoms, provided that at least one of R₂ and R₃ and at least oneof R₄ and R₅ are alkyl; (d) in the alkyl groups constituting R₁ to R₅ ;(i) the average number of carbon atoms is between about 12 and 26; (ii)not more than about 10 mole percent of said alkyl groups have less than12 carbon atoms and not more than about 10 mole percent of said alkylgroups have more than 26 carbon atoms; and (iii) the alkyl groups areessentially linear; (e) n is a number of at least about 3; and (f) thepolymer has a number average molecular weight of at least about 4,500and a molecular weight distribution of at least about 1.5.

In another aspect of the the present invention linear backbones arecrosslinked during formation with comonomer, which preferably can beeither a trifunctional comonomer having the formula: ##STR4## wherein R₆and R₇ can be hydrogen, alkyl, aryl, alkoxy, aryloxy, alkyl mercapto, orhalogen; or a tetrafunctional comonomer having the formula: ##STR5##wherein R₈ can be hydrogen, alkyl, aryl, alkoxy, aryloxy, alkylmercapto, or halogen.

In accordance with another aspect of the present invention, polymericadditives are provided by reacting alkylated phenol represented by theformula: ##STR6## wherein R represents essentially linear alkyl havingfrom 6 to 50 carbon atoms in which the average number of such carbonatoms in all of the alkyl groups is between about 16 and 22, wherein notmore than about 10 mole % of the alkyl groups have less than 16 carbonatoms and not more than about 10 mole % of the alkyl groups have morethan 22 carbon atoms, with a sulfurizing agent selected from the groupconsisting of elemental sulfur and sulfur-containing compounds havingthe formula S_(x) Cl₂, wherein x is 1 or 2, and optionally comonomerselected from formulas (II) and (III) above.

In accordance with another aspect of the present invention, a method forpreparing these polymeric compositions is provided.

In accordance with a preferred method of the present invention, thecondensation step is conducted in the presence of the trifunctional ortetrafunctional comonomer components discussed above.

In a still further aspect of the present invention, hydrocarbon oilcompositions containing these polymeric additives are provided.

DETAILED DESCRIPTION OF THE INVENTION

The additives of the present invention comprise fuel oil and lubricatingoil flow improvers which are effective and employed for modification ofthe size, number, and growth of wax crystals in various hydrocarbonoils, including fuel oils and lubricating oils, so as to impart improvedlow temperature flow properties to these oils, and which are alsoeffective for inhibiting the oxidation of these hydrocarbon oils. Mostparticularly, when used in connection with lubricating oil compositions,these lubricating oil additives are also effective to improve the lowtemperature handling, pumpability, and/or vehicle operability asmeasured by such tests as pour point and mini-rotary viscometry (MRV),and they are effective to reduce the extent of oxidation of theselubricating oils with time. When used in connection with fuels, such asmiddle distillate petroleum fuels, as well as diesel fuels, heating oilsand the like, these fuel oil flow improvers are also effective toimprove the low temperature handling characteristics thereof, as mostparticularly measured by such tests as cloud point and pour point tests.

The additive compositions of the present invention are prepared by thealkylation of phenol with specified more readily available and lessexpensive alpha-olefins, or blends thereof, under conditions sufficientto impart essential linearity to the alkyl groups of the alkylate,followed by condensation with a sulfurizing agent so as to producepolymers having certain specified molecular weights. More particularly,the use of the specific linear alpha-olefins which are set forth belowin the manner described results in superior lubricating oil and fuel oilflow improvers relative to the alkyl phenol-sulfur condensates in theprior art, and which also exhibit significant antioxidant properties. Aswill be demonstrated, these particular polymers are particularly andunexpectedly superior in terms of their ability to co-crystalize withthe wax crystals in these hydrocarbon oils which again havemulti-functional characteristics.

The particular alkyl phenol-sulfur condensates which form the basicpolymers of the present invention are generally produced by an initialalkylation step, followed by condensation with the sulfurizing agent.

Alkylation of the phenol is initially conducted with a linearalpha-olefin or blend of linear alpha-olefins which are terminalolefins, as contrasted to internal olefins. In this manner, it ispossible to produce final polymers in which the alkyl group attached tothe benzene ring is essentially linear. By "essentially linear" is meantgreater than 35, preferably at least 40, and most preferably at least 50mole percent of the alkyl groups derived from the olefin alkylatingagent (exclusive of the alkyl groups of any optional tri-ortetrafunctional component described hereinafter for molecular weightenhancement) and attached to the aromatic ring of the phenol group inthe alkylated product is linear, except for a methyl group pendant fromthe carbon attached to that aromatic ring. More specifically, sinceterminal alpha-olefins are employed for the alkylation of phenol inaccordance herewith, the terminal olefins will attach to the aromaticring at the beta carbon thereof, thereby leaving the alpha carbon as amethyl group pendant from the beta carbon of the original olefin. Thus,expressed differently, "essentially linear" means greater than 35 molepercent of the alkyl groups of the alkylated phenol are alpha methylsubstituted linear alkyl. The primary alkyl phenol product desired fromthis alkylation step (after rearrangement as discussed hereinafter) willbe linear to at least that extent.

More specifically, the initial alkylation step itself is an exothermicreaction of phenol with these particular linear terminal alpha-olefins.This reaction can thus be shown as follows: ##STR7## and in whichreaction R is linear alkyl, and R' and R" are linear alkyl groupsderived in whole or in part from R. This exothermic reaction is thus asimple cationic reaction resulting in a somewhat complex product. In theideal reaction the olefin forms a carbonium ion species as a result ofthe presence of acidic conditions and temperatures. This cation can thenreadily react with phenol at either the ortho or para positions. Withoutrearrangement, the carbonium ion species will attach to the aromaticring at the beta carbon of the olefin, and R' will thus constitute apendant methyl group derived from the alpha carbon of the originalolefin, with R" constituting the remainder of the linear alkyl chainoriginally defined by R. In reality, however, many side reactions arepossible. Thus, the cation can revert back to the olefin or rearrangefurther down the linear chain, thereby producing attachment to thearomatic ring at a more internal carbon atom, and causing the length ofR' to increase, and R" to decrease in length correspondingly. It hasbeen found that if these rearrangements are too extensive, they willlead to the production of inferior products which would not suitablyinteract with the wax crystals of the lubricating oil or fuel oil towhich they are eventually added.

It is therefore critical to the present invention to minimize theserearrangements and to maximize the attachment of the alkyl groups at the2-position (i.e., beta carbon of the original linear olefin). It hasthus been found that there are methods to minimize such rearrangement,and they primarily include carrying out the alkylation process at lowerreaction temperatures as opposed to elevated reaction temperatures. Moreparticularly, although the alkylation process itself can generally beconducted at temperatures of between about 50° and 200° C., it is mostimportant to employ alkylation temperatures of at or below about 100°C., preferably at or below 90° C., e.g., typically between about 50° and100° C., and preferably between about 50° and 90° C., to minimizerearrangement.

It has also been observed that rearrangement is more likely to occur atthe para position than the ortho position. This is probably a result ofa steric factor which permits greater accommodation of rearrangement atthe para position to the hydroxyl group. Accordingly, the definition of"essentially linear" accounts for, and expresses the permissible limitsof, the above-discussed autogenous rearrangement in forming the alkylateproduct. In short, "essentially linear" expresses the maximum degree ofacceptable branching in the alkylate product which can be tolerated whenstarting with linear alpha-olefins. The degree of rearrangement istypically determined by ¹ H-NMR and/or by high pressure liquidchromatography.

Another critical aspect of the present invention is the carbon numberand carbon number distribution of olefins employed for alkylation.

The particular linear alpha-olefins used in connection with thealkylation step of the present invention are, as indicated above,crucial to the manufacture of the proper additives for use herein. Inparticular, these linear alpha-olefins have the formula CH₂ =CH--R, inwhich R is straight chain alkyl having between about 4 and about 48carbon atoms, and in which the specific alpha-olefin or mixture ofalpha-olefins used for this alkylation has an average carbon number (ona molar basis for mixtures of olefins) of between about 12 and 26 (e.g.14 and 24), preferably between about 16 and 22 (e.g., 17 and 21, or 16and 19), and most preferably between about 18 and 20.

Moreover, the olefin mixture should not contain more than about 10 molepercent, preferably not more than about 5 mole percent, and mostpreferably not more than about 2 mole percent of alpha-olefins havingindependently: (a) less than about 12, preferably not less than about14, and most preferably not less than about 16 carbon atoms; and (b) notmore than about 26, preferably not more than about 24, and mostpreferably not more than about 22 carbon atoms. These proportionalrequirements are thereby incorporated into, and embodied in, the finalcondensate polymer.

The particular average carbon number range which is most desirable willdepend upon the ultimate environment of the alkyl phenol condensatewhich is produced hereby. That is, when used in connection with fuel oilformulations, additives in accordance with the present invention willpreferably utilize a slightly lower average carbon number for these Rgroups.

More particularly, in connection with such fuel oils, including dieselfuels and heating oils, to maximize cloud point reduction an averagecarbon number of about C₁₈ is most desired, while to maximize pour pointreduction an average carbon number of about C₁₆ is most desired.

On the other hand, in connection with lubricating oil compositions theaverage carbon number for maximizing pour point reduction is an averagecarbon content of from about C₁₈ to C₂₀.

Moreover, within each class of hydrocarbon oils, i.e., fuel orlubricating oil, each specific hydrocarbon oil can be associated with anoptimum average carbon number for the R group (also referred to hereinas the alkylate average carbon number) to achieve maximum cloud point orpour point depressancy relative to the base oil without any additive.Optimum pour depressancy will typically be achieved by an average carbonnumber that is lower than that needed to achieve optimum cloud pourpoint depressancy for a given hydrocarbon oil.

While the molecular weight and molecular weight distribution (M_(w)/M_(n)) of the condensate polymer, degree of branching, andconcentration of the condensation polymer in the hydrocarbon oil allaffect, and are important for achieving low temperature flowperformance, the two most dominant factors are the optimum alkylateaverage carbon number and the essential linearity of the alkyl group.

It is also believed that in any given situation the use of a range ofalpha-olefins surrounding the optimum average carbon number is superiorto the use of a single alpha-olefin having that number of carbon atoms.In any event, the most preferred alpha-olefins for use herein will thusinclude 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene,1-tetracosene, and mixtures thereof.

A further important factor in conducting the alkylation reaction is theminimization of monofunctional alkylation product (e.g., most dialkylateproducts), and the maximization of difunctional alkylate products (e.g.,mono alkylates) in the phenol alkylation reaction. As discussedhereinafter, the final alkyl phenol sulfur condensation product issynthesized to possess certain minimum requirements in terms ofmolecular weight and molecular weight distribution. If the alkylatedphenol product mixture employed for condensation contains too muchmonofunctional dialkylate, then the final condensation polymer will notmeet such requirements. This stems from the fact that when a secondalkyl group attaches to the phenol to yield a 2,4- or 2,6-dialkylphenol, it results in a monofunctional dialkylate molecule which, isreacted with a growing polymer chain, would terminate chain growth inthe following manner: ##STR8##

More specifically, the functionality of the alkylated-phenol reactionproduct expresses the number of available reactable sites, which remainon the alkylated phenol after alkylation, that can participate in thepolymerization reaction through propagation of a growing polymer chain.The only freely reactable sites on an unsubstituted phenol molecule forpurposes of polymerization are the 2-, 4-, and 6- carbons of the phenolaromatic ring. Thus, unsubstituted phenol is a trifunctional molecule.If monoalkylation occurs at only one of the 2-, 4-, or 6- positions, theresulting monoalkylate is said to be difunctional, since one of thereactable sites has been eliminated through substitution of an alkylgroup thereon. Similarly, the substitution of alkyl groups at any two ofthe 2-, 4-, or 6- carbons of the phenol molecule through dialkylationwill result in the formation of a monofunctional dialkylate product.Thus, 2,4-dialkyl phenol and 2,6-dialkyl phenol are monofunctionaldialkylates which will lead to chain termination, and thereby limitpolymer molecular weights. While 2,5-dialkyl phenol and 3,5-dialkylphenol are difunctional and trifunctional dialkyl monomers,respectively, such monomers do not normally form under typicalalkylation conditions, because such formation would involve reaction atnormally unreactive sites. Consequently, one seeks to minimizedialkylation generally, as most dialkylation leads to formation ofmonofunctional monomer. Thus, reference to dialkylation herein as beingundesirable is technically a reference only to dialkylation which yieldsmonofunctional dialkylate.

An equation relating the maximum degree of polymerization (DP) to theextent of reaction (ρ) and the functionality (f) of the reactants isreferred to as the Modified Carothers Equation:

    DP=2/(2-ρf)

This equation can be used to show that a monofunctional dialkylatemonomer severely limits the maximum degree of polymerization in thealkyl phenolsulfur condensation reaction.

As will be discussed hereinafter, the use of separately synthesized tri-and tetrafunctional comonomers can be employed to increase the molecularweight of the final condensation polymer and/or to compensate for thepresence of monofunctional dialkylate monomer.

Thus, the target molecular weights described hereinafter can be suitablyachieved by controlling the amount of difunctional (e.g., monoalkylate)monomer to be typically at least about 80 mole %, and preferably atleast about 85 mole %, and most preferably at least about 90 mole %, andtypically from about 80 to about 100 mole %, preferably from about 85 to100 mole %, and most preferably from about 90 to 100 (e.g., 95 to 100)mole %, based on the total moles of alkylate monomer in the monomermixture intended for polymerization.

Correspondingly, the amount of monofunctional dialkylate monomer whichcan be tolerated will typically range from about 0 to about 20 mole %,preferably from about 0 to about 15 mole %, and most preferably fromabout 0 to about 10 (e.g. 0 to about 5) mole % based on the moles ofmonomer in the alkylate monomer mixture.

High functionality monomers, such as the tri- and tetrafunctionalcomonomers described hereinafter, are typically employed in collectiveamounts of from about 0 to about 10 mole %, preferably from about 2 toabout 8 mole %, and most preferably from about 3 to about 5 mole %,based on the total moles of alkylate monomer in the alkylate monomermixture.

One way to minimize dialkylation in attempting to meet the condensationpolymer molecular weight targets specified hereinafter is to employexcess phenol relative to the olefin for the alkylation reaction.Accordingly, effective molar ratios of phenol to olefin can varytypically rom about 2:1 to about 10:1 (or higher), preferably from about2:1 to about 5:1. From a process standpoint, however, too much of anexcess of phenol can be disadvantageous because of the need to removethe excess phenol from alkylation product after alkylation is completed.

Thus, it has been found that certain zeolite catalysts as describedhereinafter permit one to lower the phenol:olefin molar ratio to lessthan about 2:1, preferably between about 1.7:1 and about 1:1 and stillachieve minimization of dialkylation. This low ratio extremelysimplifies unreacted phenol recovery.

The alkylation reaction can generally be accomplished, within the aboveparameters, by a number of techniques which are well known to thoseskilled in this art. One particularly suitable technique is by using theFriedel-Crafts reaction which occurs in the presence of a Lewis acidcatalyst, such as boron trifluoride and its complexes with ethers,phenols, hydrogen fluoride, etc., aluminum chloride, aluminum bromide,and zinc dichloride, etc. Methods and conditions for carrying out suchreactions are well known to those skilled in this art, and reference ismade, for example, to the discussion in the article entitled "Alkylationof Phenols," in Kirk-Othmer Encyclopedia of Chemical Technology, 2ndEdition, Vol. 1, pp. 894-895, Interscience Publishers, Division of JohnWiley and Company, New York, 1963, which is incorporated herein byreference thereto. A particularly preferred catalyst for use in suchalkylation reactions is designated Amberlyst 15 by the Rohm and HaasCompany. This catalyst is included among the strongly acidicmacroreticular resins patented under U.S. Pat. No. 4,224,415. This resinis itself composed of long chains of polystyrene locked together bydivinylbenzene crosslinks into a three-dimensional, insoluble polymericphase called a matrix, on which are attached sulfonic acid groups (--SO₃H). Amberlyst 15 possesses high acidity (4.7 meq/g), high porosity (32%)and high surface area (45 m² /g).

In a highly preferred method for carrying out the alkylation reactionhereof a zeolite catalyst is employed for use in the selectiveproduction of the desired mono-alkylate. More particularly, crystallinezeolites are used which have high silica to alumina ratios and whichhave effective pore sizes of between about 6 and 8 Angstroms, andinclude a number of commercial zeolite catalysts, such a LZ-Y82 catalystmanufactured by Union Carbide Corporation. In any event, a generaldescription of these zeolites is set forth in Young, U.S. Pat. No.4,283,573, which is incorporated herein by reference thereto. Ingeneral, these zeolites have a crystal structure which provides accessto and egress from the intracrystalline free space of the zeolites byvirtue of having channels or networks of pores, the openings of whichagain preferably have a major dimension, or a free pore diameter, ofbetween about 6Å and about 8Å. These zeolites are also characterized bypore apertures of about a size as would be provided by 12-member ringsof silicon and aluminum atoms. The preferred types of zeolites for usein this invention possess a silica to alumina molar ratio of from about3:1 to about 6:1. This ratio represents, as closely as possible, theratio in the rigid anionic framework of the zeolite crystal.Furthermore, these preferred zeolites will have a high surface area,such as about 625 m² /g. The use of these zeolite catalysts thus permitsone to eliminate the expensive and difficult distillation step requiredto separate the mono-alkylate from the di-alkylate produced with theacid-type catalysts previously utilized.

In connection with the alkylated phenol product, the use of a linearalpha-olefin or a mixture of linear alpha-olefins gives a ratio of orthoto para attachments on the phenol of about 2:1. In contrast with thealkylated phenol product of this reaction, the use of a branchedinternal olefin or a mixture of branched internal olefins gives a ratioof ortho to para attachments on phenol of about 1:18. However,essentially linear alkyl groups attached either ortho or para to thehydroxy group perform equally well.

The next step in the preparation of the polymer additives of the presentinvention is the actual polymerization or condensation reaction. Thereaction itself is a condensation of the above-described alkyl phenol inthe presence of a sulfurizing agent. The sulfurizing agent is definedherein to be any compound or element which introduces --(S)_(x) --bridging groups between the alkylated phenol monomer groups, wherein xis a number of from 1 to about 8. Thus, the condensation reaction can beconducted with elemental sulfur or a halide thereof such as sulfurmonochloride or, more preferably, sulfur dichloride. If elemental sulfuris used, this reaction is effected by heating the alkyl phenol compoundat between about 50° and 250° C., and usually at least about 160° C. Theuse of elemental sulfur will typically yield a mixture of bridginggroups --(S)_(x) -- as described above. If sulfur halide is used, thisreaction is effected by heating the alkyl phenol compound at betweenabout 50° and 120° C., and usually at about 80° C. Optimally, thereaction can be conducted in the presence of a suitable diluent. Thediluent can generally comprise a substantially inert organic diluentsuch as mineral oil or an alkane, ketone, ether, ether alcohol, or thelike. In any event, this is conducted for a period of time sufficient toeffect substantial reaction. It is generally preferred to employ betweenabout 0.1 and 5 moles of the alkyl phenol material per equivalent ofsulfurizing agent.

Where elemental sulfur is used as the sulfurizing agent, it isfrequently preferred to use a basic catalyst such as sodium hydroxide oran organic amine, preferably a heterocyclic amine (e.g., morpholine).

Particularly where sulfur halides are used as the sulfurizing agent, itis frequently preferred to use an acid acceptor, such as sodiumhydroxide, calcium carbonate or the like, to react with the hydrogenhalide evolved therein.

Pressure is not a critical factor, and can be atmospheric or below, upto 1000 psi or higher. Atmospheric pressure is preferred forconvenience, and the pressure should be sufficient to maintain thereactants in the liquid phase.

The reactants, together with catalyst and any diluent which is employed,can thus be charged to a reactor and reacted under the conditions setforth above. The crude reaction product mixture can then be cooled,neutralized, water-washed to remove any catalyst, dried, and thenstripped to remove excess reactant, any unreacted materials, and anydiluent that may have been used.

The condensation reaction is conducted in a manner and under conditionssufficient to achieve or surpass certain minimum number average andweight average molecular weight targets. Accordingly, the condensationreaction is conducted to impart to the final polymer a number averagemolecular weight (M_(n)) as determined by vapor-phase osmometry of atleast about 3,000 (e.g., at least about 4,000), preferably at leastabout 5,000, and most preferably at least about 7,000, and typicallyfrom about 3,000 to about 60,000 (e.g., 4,000 to 60,000), preferablyfrom about 5,000 to about 30,000, most preferably from about 7,000 toabout 20,000, and a weight average molecular weight (M_(w)) asdetermined by gel permeation chromatography, of at least about 4,500(e.g., at least about 5,000), preferably at least about 6,000, andtypically from about 4,500 to about 100,000, preferably from about10,000 to about 70,000 (e.g., 6,000 to about 35,000), and mostpreferably from about 20,000 to about 50,000.

The maximum number and weight average molecular weights are limited onlyby the solubility of the condensate polymer in the particularhydrocarbon basestock in question.

It is most preferred that these polymers have a ratio of weight averagemolecular weight to number average molecular weight (M_(w) /M_(n)),commonly referred to as molecular weight distribution, of greater thanabout 1.5, preferably greater than about 2.0, and most preferablygreater than about 2.5, and typically from about 1.5 to about 34,preferably from about 2.0 to about 24, and most preferably from about3.0 to about 7.0. Generally, the higher the weight average molecularweight, the better suited or more effective these polymers are forimproving the flow properties of various hydrocarbon oils in accordancewith the present invention.

While number average molecular weight (M_(n)) can conveniently also bedetermined by gel permeation chromatography (GPC), it is considered thatVPO techniques are more accurate, although the M_(n) by the GPCtechnique will typically approximate M_(n) by VPO within ±1000, moretypically ±500.

In one embodiment, polymers or condensates which are thus produced inaccordance with this process can be represented by the followingformula: ##STR9## in which x is an integer of typically from 1 to about8, preferably from about 1 to about 5, and most preferably from about 1to about 2, R₁ represents attached essentially linear alkyl groupsdiscussed above derived from the linear alpha-olefin having form about 6to 50 carbon atoms, in which the average number of carbon atoms in allof the groups constituting R₁ is between about 12 and 26, preferablybetween about 16 and 22, and most preferably between about 18 and 20,and in which no more than about 10 mole percent, etc. of alkyl groupshave less than 12 carbon atoms and no more than about 10 mole percent,etc. of alkyl groups have more than 26 carbon atoms; R₂, R₃, R₄ and R₅independently can represent hydrogen or alkyl as described in connectionwith R₁, with the proviso that at least one of R₂ and R₃ is said alkyland at least one of R₃ and R₄ is said alkyl. The hydroxy group of thephenol will be located on an aromatic carbon which is adjacent to acarbon on which at least one of the --(S)_(x) -- groups is attached.

The value of n is subject to the number average molecular weight targetsdiscussed above, and the minimum value thereof expressed thereinafterwill consequently vary depending on the average carbon number of theolefins employed for alkylation, the average value of x, and the numberof repeating units controlled by n necessary to achieve such M_(n)values when accounting for said olefin average carbon number and theaverage value of x.

Accordingly, n is a number which, subject to the above constraints, willtypically be at least 3 (e.g., at least 5), preferably at least 8 (e.g.,at least 10), and most preferably at least 12, and can vary typicallyfrom about 5 to about 80, preferably from about 10 to about 60, and mostpreferably from about 15 to about 30.

As indicated above, it can be somewhat difficult to increase themolecular weights of the alkylated phenol-sulfur condensates beyond acertain level because of the propensity of dialkylate monomers toterminate chain growth.

There are yet additional methods of increasing the molecular weight ofthe alkylated phenol-sulfur condensate flow improvers of the presentinvention. In this method, the polymerization step is carried out in theadditional presence of trifunctional or tetrafunctional comonomer(functionality being reactable sites) so as to produce an ultimatecondensation polymer having a branched backbone rather than linearbackbone as shown in formula (I) hereabove wherein said linear backbonesare crosslinked through said trifunctional and/or tetrafunctionalcomonomers.

In particular, a trifunctional comonomer having the following formulacan be employed: ##STR10## in which R₆ and R₇ can be hydrogen, alkyl,aryl, alkoxy, aryloxy, alkyl mercapto, and halogen. More particularly,it is preferred that R₆ and R₇ include branched or straight chain alkylgroups, preferably straight chain, such as C₁ through C₃₀ alkyl,preferably methyl, C₆ through C₁₄ aryl, C₁ through C₂₂ alkoxy, C₆through C₁₄ aryloxy, C₁ to C₃₀ alkyl mercapto, and preferably halogenssuch as chlorine and bromine.

As discussed above, 3,5-dialkylate is difficult to achieve under normalalkylation conditions. Consequently, a variety of methods well known inthe art can be employed to achieve 3,5-dialkylation. One such methodinvolves a thallation reaction wherein, for example, 1,3-dimethylbenzene is contacted with a thallium trifluoro acetate catalyst to causestereo specific oxidation to 3,5-dimethyl phenol.

Representative examples of trifunctional monomers include phenol,m-cresol, 3,5-xylenol, m-phenyl phenol, m-methoxyphenol, orcinol, andm-methyl mercapto phenol, while phenol is preferred.

For example, when phenol is employed as the trifunctional monomer, thena portion of the branched backbone can be represented by the followingformula with an asterisk indicating the original phenol trifunctionalmonomer: ##STR11## It is thus possible in this manner to produce suchpolymer condensates having weight average molecular weights determinedby gel permeation chromatography of greater than about 10,000,preferably between about 10,000 and 100,000, and most preferably greaterthan about 20,000.

Even further branching is achieved with tetrafunctional monomer whichcan crosslink four linear backbones.

The tetrafunctional comonomers which can be used in the polymerizationstep of the present invention can have the formula: ##STR12## in whichR₈ independently can be the same hydrogen, alkyl, aryl, alkoxy, aryloxy,alkyl mercapto, and halogen components discussed above in connectionwith the trifunctional comonomers as formula II hereof. Representativeexamples of suitable tetrafunctional monomers include bisphenol A,bisphenol B, methylene-4,4'-bis (3,5-dibutylphenol), methylene-4,4'-bis(3,5-dimethoxyphenol), methylene-4,4'-bis (3,5-dimethylmercapto phenol),with bisphenol A being preferred. Again, in this case it is alsopossible to produce such polymer condensates having weight averagemolecular weights determined by gel permeation chromatography of greaterthan about 10,000, preferably between about 10,000 and 100,000, and mostpreferably greater than about 20,000.

The amount of such trifunctional and/or tetrafunctional comonomeremployed in the polymerization or condensation step of the presentinvention must, however, be limited to a certain extent. That is, theamount of comonomer present should be less than about 10 wt. % of acombination of the alkylated phenol and the sulfurizing agent, andpreferably less than about 8 wt. %. It has thus been found that if toogreat an amount of the trifunctional and/or tetrafunctional comonomer ispresent, that material tends to crosslink to the extent that aninsoluble mass can be formed thereby. This can be avoided, however, byusing the amounts discussed above, and additionally by conducting thepolymerization in the initial presence of small amounts of thetrifunctional or tetrafunctional comonomer. Also, this comonomer can becontinuously added during the course of polymerization, thereby becomingdiluted with the polymerizing alkyl phenol composition to maintain thecomonomer as dilute as possible throughout the polymerization reaction.

It is also contemplated, although less preferred, that blends ofseparately synthesized alkyl phenol condensates meeting theaforedescribed requirements can be employed.

For purpose of discussion, when such blends are employed, the overallalkylate average carbon number for each polymer component in the blendin which the alkylate portion thereof is derived from a singlealpha-olefin, or single mixture of alpha-olefins, can also be referredto herein as the alkylate intra-molecular carbon average. However, thealkylate intra-molecular carbon average of each polymer component in theblend can then also be averaged on a molar basis to determine what isreferred to herein as the alkylate inter-molecular carbon average forthe blend.

It is believed that when the optimum alkylate average carbon number(i.e., intra-molecular average carbon number) has been determined for aparticular hydrocarbon oil, the best low temperature performance isachieved by a single polymer which possesses this optimum average carbonnumber value, rather than a blend of polymers wherein each polymercomponent in the blend possesses a non-optimum alkylate intra-molecularcarbon average, but the blend collectively possesses an alkylateinter-molecular carbon average value equal to the value of the optimumintra-molecular carbon average.

The polymer additives produced in accordance with present invention havebeen found to be useful in fuel oils and lubricating oils. The normallyliquid fuel oils are generally derived from petroleum sources, e.g.,normally liquid petroleum distillate fuels, though they may includethose produced synthetically by the Fischer-Tropsch and relatedprocesses, the processing of organic waste material or the processing ofcoal, lignite or shale rock. Such fuel compositions have varying boilingranges, viscosities, cloud and pour points, etc., according to their enduse as is well known to those of skill in the art. Among such fuels arethose commonly known as diesel fuels, distillate fuels, heating oils,residual fuels, bunker fuels, etc., which are collectively referred toherein as fuel oils. The properties of such fuels are well known toskilled artisans as illustrated, for example, by ASTM Specification D#396-73, available from the American Society for Testing Materials, 1916Race Street, Philadelphia, Pa. 19103.

Particularly preferred fuel oils include middle distillates boiling fromabout 120° to 725° F. (e.g., 375° to 725° F.), including kerosene,diesel fuels, home heating fuel oil, jet fuels, etc., and mostpreferably whose 20% and 90% distillation points differ by less than212° F., and/or whose 90% to final boiling point range is between about20° and 50° F. and/or whose final boiling point is in the range of 600°to 700° F.

The additives of this invention find their primary utility, however, inlubricating oil compositions, which employ a base oil in which theadditives are dissolved or dispersed. Such base oils may be natural or amixture of natural and synthetic oils.

Thus, base oils suitable for use in preparing the lubricating oilcompositions of the present invention include those conventionallyemployed as crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, such as automobile andtruck engines, marine and railroad diesel engines, and the like.Advantageous results are also achieved by employing the additives of thepresent invention in base oils conventionally employed in and/or adaptedfor use as power transmitting fluids such as automatic transmissionfluids, tractor fluids, universal tractor fluids and hydraulic fluids,heavy duty hydraulic fluids, power steering fluids and the like. Gearlubricants, industrial oils, pump oils and other lubricating oilcompositions can also benefit from the incorporation therein of theadditives of the present invention.

Thus, the additives of the present invention may be suitablyincorporated into mixtures of natural and synthetic base oils providedthese mixtures include at least about 80 wt. % of natural base oil.Suitable synthetic base oils for use in these mixtures include alkylesters of dicarboxylic acids, polyglycols and alcohols;polyalpha-olefins, polybutenes, alkyl benzenes, organic esters ofphosphoric acids, polysilicone oils, etc.

Natural base oils include mineral lubricating oils which may vary widelyas to their crude source, e.g., whether paraffinic, naphthenic, mixed,paraffinicnaphthenic, and the like; as well as to their formation, e.g.,distillation range, straight run or cracked, hydrofined, solventextracted and the like.

More specifically, the natural lubricating oil base stocks which can beused in the compositions of this invention may be straight minerallubricating oil or distillates derived from paraffinic, naphthenic,asphaltic, or mixed base crudes, or, if desired, various blends of oilsmay be employed as well as residuals, particularly those from whichasphaltic constituents have been removed. The oils may be refined byconventional methods using acid, alkali, and/or clay or other agentssuch as aluminum chloride, or they may be extracted oils produced, forexample, by solvent extraction with solvents of the type of phenol,sulfur dioxide, furfural, dichlorodiethyl ether, nitrobenzene,crotonaldehyde, etc.

The lubricating oil base stock conveniently has a viscosity of typicallyabout 2.5 to about 12, and preferably about 2.5 to about 9 cSt at 100°C.

Thus, the additives of the present invention can be employed in ahydrocarbon oil (i.e., fuel oil or lubricating oil) composition whichcomprises hydrocarbon oil, typically in a major amount, and theadditive, typically in a minor amount, which is effective to impart orenhance one or more of the low temperature flow properties describedherein. Additional conventional additives selected to meet theparticular requirements of a selected type of hydrocarbon oilcomposition can be included as desired.

The additives of this invention are oil-soluble, dissolvable in oil withthe aid of a suitable solvent, or are stably dispersible materials.Oil-soluble, dissolvable, or stably dispersible as that terminology isused herein does not necessarily indicate that the materials aresoluble, dissolvable, miscible, or capable of being suspended in oil inall proportions. It does mean, however, that the additives, forinstance, are soluble or stably dispersible in oil to an extentsufficient to exert their intended effect in the environment in whichthe oil is employed. Moreover, the additional incorporation of otheradditives may also permit incorporation of higher levels of a particularpolymer adduct hereof, if desired.

Accordingly, while any effective amount of these additives can beincorporated into the fully formulated hydrocarbon oil composition, itis contemplated that such effective amount be sufficient to provide saidhydrocarbon oil composition with an amount of the additive of typicallyfrom 0.005 to 10, e.g., 0.01 to 2, and preferably from 0.025 to 0.25 wt.%, based on the weight of said composition.

The additives of the present invention can be incorporated into thehydrocarbon oil in any convenient way. Thus, they can be added directlyto the oil by dispersing, or dissolving the same in the oil at thedesired level of concentration, typically with the aid of a suitablesolvent such as toluene, cyclohexane, or tetrahydrofuran. Such blendingcan occur at room temperature or elevated temperatures. In this form theadditive per se is thus being utilized as a 100% active ingredient formwhich can be added to the oil or fuel formulation by the purchaser.Alternatively, these additives may be blended with a suitableoil-soluble solvent and/or base oil to form a concentrate, which maythen be blended with a hydrocarbon oil base stock to obtain the finalformulation. Concentrates will typically contain from about 1 to 50%, byweight of the additive, and preferably from about 10 to 30% by weight ofthe additive.

The hydrocarbon oil base stock for the additives of the presentinvention typically is adapted to perform a selected function by theincorporation of additives therein to form lubricating oil compositions(i.e., formulations).

Representative additives typically present in such formulations includeviscosity modifiers, corrosion inhibitors, oxidation inhibitors,friction modifiers, dispersants, anti-foaming agents, anti-wear agents,pour point depressants, detergents, rust inhibitors and the like.

Viscosity modifiers, or viscosity index (V.I.) improvers impart high andlow temperature operability to the lubricating oil and permit it toremain shear stable at elevated temperatures and also exhibit acceptableviscosity or fluidity at low temperatures. These viscosity indeximprovers are generally high molecular weight hydrocarbon polymersincluding polyesters. The V.I. improvers may also be derivatized toinclude other properties or functions, such as the addition ofdispersancy properties.

These oil soluble V.I. polymers will generally have number averagemolecular weights of from about 40,000 to 1,000,000, preferably fromabout 40,000 to about 300,000, as determined by gel permeationchromatography or membrance osmometry.

Examples of suitable hydrocarbon polymers include homopolymers andinterpolymers of two or more monomers of C₂ to C₃₀, e.g., C₂ to C₈olefins, including both alpha-olefins and internal olefins, which may bestraight or branched, aliphatic, aromatic, alkylaromatic,cycloaliphatic, etc. Frequently they will be of ethylene with C₃ to C₃₀olefins, particularly preferred being the copolymers of ethylene andpropylene. Other polymers can be used such as polyisobutylenes,homopolymers and interpolymers of C₆ and higher alpha-olefins, atacticpolypropylene, hydrogenated polymers and copolymers and terpolymers ofstyrene, e.g., with isoprene and/or butadiene.

More specifically, other hydrocarbon polymers suitable as viscosityindex improvers include those which may be described as hydrogenated orpartially hydrogenated homopolymers, and random, tapered, star, or blockinterpolymers (including terpolymers, tetrapolymers, etc.) of conjugateddienes and/or monovinyl aromatic compounds with, optionally,alpha-olefins or lower alkenes, e.g., C₃ to C₁₈ alpha-olefins or loweralkenes. The conjugated dienes include isoprene, butadiene,2,3-dimethylbutadiene, piperylene and/or mixtures thereof, such aisoprene and butadiene. The monovinyl aromatic compounds include any ofthe following, or mixtures thereof, vinyl di- or polyaromatic compounds,e.g., vinyl naphthalene, but are preferably monovinyl monoaromaticcompounds, such as styrene or alkylated styrenes substituted at thealpha-carbon atoms of the styrene, such as alpha-methylstyrene, or atring carbons, such as o-, m-, p-methylstyrene, ethylstyrene,propylstyrene, isopropyl-styrene, butylstyrene, isobutylstyrene,tert-butylstyrene (e.g., p-tert-butylstyrene). Also included arevinylxylenes, methylethyl styrenes and ethylvinylstyrenes. Alpha-olefinsand lower alkenes optionally included in these random, tapered and blockcopolymers preferably include ethylene, propylene, butene,ethylene-propylene copolymers, isobutylene, and polymers and copolymersthereof. As is also known in the art, these random, tapered and blockcopolymers may include relatively small amounts, that is less than about5 moles, of other copolymerizable monomers such as vinyl pyridines,vinyl lactams, methacrylates, vinyl chloride, vinylidene chloride, vinylacetate, vinyl stearate, and the like.

Specific examples include random polymers of butadiene and/or isopreneand polymers of isoprene and/or butadiene and styrene. Typical blockcopolymers include polystyrene-polyisoprene, polystyrene-polybutadiene,polystyrene-polyethylene, polystyrene-ethylene propylene copolymer,polyvinyl cyclohexane-hydrogenated polyisoprene, and polyvinylcyclohexane-hydrogenated polybutadiene. Tapered polymers include thoseof the foregoing monomers prepared by methods known in the art.Star-shaped polymers typically comprise a nucleus and polymeric armslinked to said nucleus, the arms being comprised of homopolymer orinterpolymer of said conjugated diene and/or monovinyl aromaticmonomers. Typically, at least about 80% of the aliphatic unsaturationand about 20% of the aromatic unsaturation of the star-shaped polymer isreduced by hydrogenation.

Representative examples of patents which disclose such hydrogenatedpolymers or interpolymers include U.S. Pat. Nos. 3,312,621; 3,318,813;3,630,905; 3,668,125; 3,763,044; 3,795615; 3,835,053; 3,838,049;3,965,019; 4,358,565; and 4,557,849, the disclosures of which are hereinincorporated by reference.

The polymer may be degraded in molecular weight, for example bymastication, extrusion, oxidation or thermal degradation, and it may beoxidized and contain oxygen. Also included are derivatized polymers suchas post-grafted interpolymers of ethylene-propylene with an activemonomer such as maleic anhydride which may be further reacted with analcohol, or amine, e.g., an alkylene polyamine or hydroxy amine, e.g.,see U.S. Pat. Nos. 4,089,794; 4,160,739; 4,137,185; or copolymers orethylene and propylene reacted or grafted with nitrogen compounds suchas shown in U.S. Pat. Nos. 4,068,056; 4,068,058; 4,146,489; and4,149,984.

Suitable hydrocarbon polymers are ethylene interpolymers containing from15 to 90 wt. % ethylene, preferably 30 to 80 wt. % of ethylene and 10 to85 wt. %, preferably 20 to 70 wt. % of one or more C₃ to C₈,alpha-olefins. While not essential, such interpolymers preferably have adegree of crystallinity of less than 10 wt. %, as determined by X-rayand differential scanning calorimetry. Copolymers of ethylene andpropylene are most preferred. Other alpha-olefins suitable in place ofpropylene to form the copolymer, or to be used in combination withethylene and propylene, to form a terpolymer, tetrapolymer, etc.,include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc.; alsobranched chain alpha-olefins, such as 4-methyl-1-pentene,4-methyl-1-hexene, 5-methyl-1-pentene, 4,4-dimethyl-1-pentene, and6-methyl-1-heptene, etc., and mixtures thereof.

Terpolymers, tetrapolymers, etc., of ethylene, said C₃₋₈ alpha-olefin,and a non-conjugated diolefin or mixtures of such diolefins may also beused. The amount of the non-conjugated diolefin generally ranges fromabout 0.5 to 20 mole percent, preferably from about 1 to about 7 molepercent, based on the total amount of ethylene and alpha-olefin present.

Corrosion inhibitors, also known as anti-corrosive agents, reduce thedegradation of the metallic parts contacted by the lubricating oilcomposition. Illustrative of corrosion inhibitors are phosphosulfurizedhydrocarbons and the products obtained by reaction of aphosphosulfurized hydrocarbon with an alkaline earth metal oxide orhydroxide, preferably in the presence of an alkylated phenol or of analkylphenol thioester, and also preferably in the presence of carbondioxide. Phosphosulfurized hydrocarbons are prepared by reacting asuitable hydrocarbon such as a terpene, a heavy petroleum fraction of aC₂ to C₆ olefin polymer such as polyisobutylene, with from 5 to 30 wt. %of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature in therange of about 66° to about 316° C. Neutralization of thephosphosulfurized hydrocarbon may be effected in the manner taught inU.S. Pat. No. 1,969,324.

Oxidation inhibitors, or antioxidants, reduce the tendency of mineraloils to deteriorate in service which deterioration can be evidenced bythe products of oxidation such as sludge and varnish-like deposits onthe metal surfaces, and by viscosity growth. Such oxidation inhibitorsinclude alkaline earth metal salts of alkylphenolthioesters havingpreferably C₅ to C₁₂ alkyl side chains, e.g., calcium nonylphenolsulfide, barium t-octylphenyl sulfide, dioctylphenylamine,phenylalphanaphthylamine, phospho- sulfurized or sulfurizedhydrocarbons, etc.

Other oxidation inhibitors or antioxidants useful in this inventioncomprise oil-soluble copper compounds. The copper may be blended intothe oil as any suitable oil-soluble copper compound. By oil soluble itis meant that the compound is oil soluble under normal blendingconditions in the oil or additive package. The copper compound may be inthe cuprous or cupric form. The copper may be in the form of the copperdihydrocarbyl thio- or dithio-phosphates. Alternatively, the copper maybe added as the copper salt of a synthetic or natural carboxylic acid.Examples of same thus include C₁₀ to C₁₈ fatty acids, such as stearic orpalmitic acid, but unsaturated acids such as oleic or branchedcarboxylic acids such as napthenic acids of molecular weights of fromabout 200 to 500, or synthetic carboxylic acids, are preferred, becauseof the improved handling and solubility properties of the resultingcopper carboxylates. Also useful are oil-soluble copper dithiocarbamatesof the general formula (RR'NCSS)_(n) Cu (where n is 1 or 2 and R and R'are the same or different hydrocarbyl radicals containing from 1 to 18,and preferably 2 to 12, carbon atoms, and including radicals such asalkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.Particularly preferred as R and R' groups are alkyl groups of from 2 to8 carbon atoms. Thus, the radicals may, for example, be ethyl, n-propyl,i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl,n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl,cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc. In order toobtain oil solubility, the total number of carbon atoms (i.e., R and R')will generally be about 5 or greater. Copper sulphonates, phenates, andacetylacetonates may also be used.

Exemplary of useful copper compounds are copper Cu^(I) and/or Cu^(II)salts of alkenyl succinic acids or anhydrides. The salts themselves maybe basic, neutral or acidic. They may be formed by reacting (a)polyalkylene succinimides (having polymer groups of M_(n) of 700 to5,000) derived from polyalkylene-polyamines, which have at least onefree carboxylic acid group, with (b) a reactive metal compound. Suitablereactive metal compounds include those such as cupric or cuproushydroxides, oxides, acetates, borates, and carbonates or basic coppercarbonate.

Examples of these metal salts are Cu salts of polyisobutenyl succinicanhydride, and Cu salts of polyisobutenyl succinic acid. Preferably, theselected metal employed is its divalent form, e.g., Cu⁺². The preferredsubstrates are polyalkenyl succinic acids in which the alkenyl group hasa molecular weight greater than about 700. The alkenyl group desirablyhas a M_(n) from about 900 to 1,400, and up to 2,500, with a M_(n) ofabout 950 being most preferred. Especially preferred is polyisobutylenesuccinic anhydride or acid. These materials may desirably be dissolvedin a solvent, such as a mineral oil, and heated in the presence of awater solution (or slurry) of the metal bearing material. Heating maytake place between 70° and about 200° C. Temperatures of 110° C. to 140°C. are entirely adequate. It may be necessary, depending upon the saltproduced, not to allow the reaction to remain at a temperature aboveabout 140° C. for an extended period of time, e.g., longer than 5 hours,or decomposition of the salt may occur.

The copper antioxidants (e.g., Cu-polyisobutenyl succinic anhydride,Cu-oleate, or mixtures thereof) will be generally employed in an amountof from about 50 to 500 ppm by weight of the metal, in the finallubricating or fuel composition.

Friction modifiers serve to impart the proper friction characteristicsto lubricating oil compositions such as automatic transmission fluids.

Representative examples of suitable friction modifiers are found in U.S.Pat. No. 3,933,659 which discloses fatty acid esters, amides, andtertiary amines, e.g., hydroxyamines; U.S. Pat. No. 4,176,074 whichdescribes molybdenum complexes of polyisobutyenyl succinicanhydride-amino alkanols; U.S. Pat. No. 4,105,571 which disclosesglycerol esters of dimerized fatty acids; U.S. Pat. No. 3,779,928 whichdiscloses alkane phosphonic acid salts; U.S. Pat. No. 3,778,375 whichdiscloses reaction products of a phosphonate with an oleamide; U.S. Pat.No. 3,852,205 which discloses S-carboxyalkylene hydrocarbyl succinimide,S-carboxyalkylene hydrocarbyl succinamic acid and mixtures thereof; U.S.Pat. No. 3,879,306 which discloses N-(hydroxyalkyl)alkenyl-succinamicacids or succinimides; U.S. Pat. No. 3,932,290 which discloses reactionproducts of di- (lower alkyl) phosphites and epoxides; and U.S. Pat. No.4,028,258 which discloses the alkylene oxide adduct of phosphosulfurizedN-(hydroxyalkyl) alkenyl succinimides; and succinate esters, or metalsalts thereof, of hydrocarbyl substituted succinic acids or anhydridesand thiobisalkanols such as described in U.S. Pat. No. 4,344,853. Thedisclosures of the above references are herein incorporated byreference.

Dispersants maintain oil insolubles, resulting from oxidation duringuse, in suspension in the fluid thus preventing sludge flocculation andprecipitation or deposition on metal parts. Suitable dispersants includehigh molecular weight alkyl succinimides, the reaction product ofoil-soluble polyisobutylene succinic anhydride with ethylene amines suchas tetraethylene pentamine and borated salts thereof.

Pour point depressants, otherwise known as lube oil flow improvers,lower the temperature at which the fluid will flow or can be poured.Such additives are well known. Typical of those additives which usefullyoptimize the low temperature fluidity of the fluid are C₈ -C₁₈dialkylfumarate vinyl acetate copolymers, polymethacrylates, and waxnaphthalene.

Foam control can be provided by an antifoamant of the polysiloxane type,e.g., silicone oil and polydimethyl siloxane.

Anti-wear agents, as their name implies, reduce wear of metal parts.Representatives of conventional anti-wear agents are zincdialkyldithiophosphate and zinc diaryldithiosphate.

Detergents and metal rust inhibitors include the metal salts ofsulphonic acids, alkyl phenols, sulfurized alkyl phenols, alkylsalicylates, napthenates and other oil-soluble mono- and di-carboxylicacids. Highly basic (viz, overbased) metal salts, such as highly basicalkaline earth metal sulfonates (especially Ca and Mg salts) arefrequently used as detergents. Representative examples of suchmaterials, and their methods of preparation, are found in co-pendingSer. No. 754,001, filed Jul. 11, 1985, the disclosure of which is herebyincorporated by reference.

Some of these numerous additives can provide a multiplicity of effects,e.g., a dispersant-oxidation inhibitor. This approach is well known andneed not be further elaborated herein.

Compositions when containing these conventional additives are typicallyblended into the base oil in amounts which are effective to providetheir normal attendant function. Representative effective amounts ofsuch additives are illustrated as follows:

    ______________________________________                                                          Wt. % a.i.                                                                              Wt. % a.i.                                        Additive          (Broad)   (Preferred)                                       ______________________________________                                        Viscosity Modifier                                                                               .01-12   .01-4                                             Corrosion Inhibitor                                                                             0.01-5    .01-1.5                                           Oxidation Inhibitor                                                                             0.01-5    .01-1.5                                           Dispersant         0.1-20   0.1-8                                             Pour Point Depressant                                                                           0.005-10  .01-2                                             Anti-Foaming Agents                                                                             0.001-3   .001-0.15                                         Anti-Wear Agents  0.001-5   .001-1.5                                          Friction Modifiers                                                                              0.01-5    .01-1.5                                           Detergents/Rust Inhibitors                                                                       .01-10   .01-3                                             Mineral Oil Base  Balance   Balance                                           ______________________________________                                    

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentratedsolutions or dispersions of the flow improver (in concentrate amountshereinabove described), together with one or more of said otheradditives (said concentrate when constituting an additive mixture beingreferred to herein as an additive-package) whereby several additives canbe added simultaneously to the base oil to form the hydrocarbon oilcomposition. Dissolution of the additive concentrate into thehydrocarbon oil may be facilitated by solvents and by mixing accompaniedwith mild heating, but this is not essential. The concentrate oradditive-package will typically be formulated to contain the flowimprover additive and optional additional additives in proper amounts toprovide the desired concentration in the final formulation when theadditive-package is combined with a predetermined amount of basehydrocarbon oil. Thus, the products of the present invention can beadded to small amounts of base oil or other compatible solvents alongwith other desirable additives to form additive-packages containingactive ingredients in collective amounts of typically from about 2.5 toabout 90%, and preferably from about 5 to about 75%, and most preferablyfrom about 8 to about 50% by weight additives in the appropriateproportions with the remainder being base oil. For safetyconsiderations, the base oil for concentrates is typically a lubricatingoil rather than a fuel oil.

The final formulations may employ typically about 10 wt. % of theadditive-package with the remainder being base oil.

All of said weight percents expressed herein are based on activeingredient (a.i.) content of the additive, and/or upon the total weightof any additive-package, or formulation which will be the sum of thea.i. weight of each additive plus the weight of total oil or diluent.

This invention will be further understood by reference to the followingexamples, wherein all parts are parts by weight and all molecularweights are either number average molecular weight determined byvapor-phase osmometry or weight average molecular weights determined bygel permeation chromatography as noted unless otherwise specified, andwhich include preferred embodiments of the invention.

The following examples are given as specific illustrations of theclaimed invention. It should be understood, however, that the inventionis not limited to the specific details set forth in the examples. Allparts and percentages in the examples, as well as in the remainder ofthe specification, are by weight unless otherwise specified.

EXAMPLE 1

As an example of the preparation of a typical alkylated phenol componentused to produce the polymer condensates of the present invention,octadecylphenol was prepared by charging into a four-necked, 5 liter,round bottom flask equipped with a mechanical stirrer, 933 grams ofphenol (9.93 moles) and 286 grams of Amberlyst-15 catalyst. The flaskwas also equipped with a reflux condenser, a thermometer, an additionfunnel, and a nitrogen inlet. This mixture was then heated to 70° C.under a blanket of nitrogen, and, with stirring, 834 grams (3.31 moles)of 1-octadecene were added dropwise over a period of about one hour. Thereaction mixture was then heated to 90° C., and this temperature wasmaintained for a period of four hours, yielding greater than 98%conversion of olefin as measured by gas chromatography. The reactionmixture was then cooled to 50° C. and filtered to remove the catalyst.The excess phenol was removed by vacuum distillation, and the yield was1,008 grams (or 88%). The product had a refractive index of 1.4859 at25° C., a viscosity of 38.0 cP at 40° C., and a hydroxyl number of 144mg KOH/gm. The infrared spectrum of the product showed absorption bandsat 830 and 750 cm⁻¹, which are characteristic of alkyl phenols. Thearomatic substitution pattern was determined by ¹³ C-NMR and showed thatthe ortho to para ratio was 2:1. The alkyl substitution pattern wasdetermined by ¹ H-NMR, and showed that the product consisted of 50 molepercent 2-substituted alkylate and 50 mole percent ≧3-substitutedalkylate. The melting point and heat of fusion of the product weredetermined by differential scanning calorimetry (DSC) to be 8.7° C. and85 J/g, respectively.

EXAMPLE 2

As another example of the preparation of the alkylated phenol used inaccordance with the present invention, Example 1 was again repeated,except that in this case a molar equivalent of 1-hexadecene wassubstituted for the 1-octadecene. The yield of hexadecylphenol was 958grams (or 91%). The product had a refractive index of 1.4881 at 25° C.,a viscosity of 34.6 cP at 40° C., and a hydroxyl number of 159 mg KOH/g.The infrared spectrum showed absorption bands at 830 and 750 cm⁻¹. Theortho to para ratio determined by ¹³ C-NMR was 2:1. The alkylsubstitution pattern determined by ¹ H-NMR showed that the productconsisted of 50 mole percent 2-substituted alkylate and 50 mole percent≧3-substituted alkylate. The melting point and heat of fusion weredetermined by DSC to be -9.9° C. and 56 J/g, respectively.

EXAMPLE 3

In this example, a preferred alkylated phenol in accordance with thepresent invention was prepared from a mixture of alpha-olefins. Thus, inthis case, into a similar four-necked, 5 liter, round-bottom flask,equipped with a mechanical stirrer, a reflux condenser, a thermometer, ajacketed addition funnel, and a nitrogen inlet, were added 933 grams ofphenol (9.93 moles) and 286 grams of Amberlyst-15 catalyst. Nine hundredseventy-three grams of a mixture of 50 mole percent 1-eicosene (C₂₀), 42mole percent 1-dococene (C₂₂), and 8 mole percent 1-tetracosene (molaraverage being C₂₁ H₄₂ [heneicosene]) was then charged to an additionfunnel that was heated to prevent the olefin mixture from solidifying.While stirring, the heated olefin mixture was added dropwise over aperiod of one hour. The reaction mixture was then heated to 90° C., andthis temperature was maintained for about five hours, giving greaterthan 97% conversion of olefin as measured by gas chromatography. Thereaction mixture was cooled to 50° C. and filtered to remove thecatalyst, and the excess phenol was subsequently removed by vacuumdistillation. The yield was 1130 grams (or 88%). The product had arefractive index of 1.4810 at 25° C. and a hydroxyl number of 122 mgKOH/g, with the infrared spectrum again showing bands at 830 and 750cm⁻¹. The ortho to para ratio determined by ¹³ C-NMR was 2:1. The alkylsubstitution pattern determined by ¹ H-NMR showed that the productconsisted of 50 mole percent 2-substituted and 50 mole percent -3-substituted alkylate. The product's melting point and heat of fusionwere determined by DSC to be 28.2° C. and 110 J/g, respectively.

EXAMPLE 4

As an example of the preparation of an alkylated phenol-sulfurcondensate polymer of the present invention, into a four-necked, 1 literround bottom flask, equipped with a mechanical stirrer, a thermometer,addition funnel, nitrogen inlet tube, and a Dean-Stark trap with areflux condenser, were charged 250 grams of octadecyl phenol produced inaccordance with Example 1. The octadecyl phenol was heated to 80° C.While stirring, 82 grams of a mixture of 76% sulfur dichloride and 24%sulfur monochloride were added over a period of about one hour, with thetemperature maintained at about 80° C. After the addition was completed,the reaction mixture was soaked for about five minutes at 80° C. andthen heated to 95° C. and sparged with nitrogen for one hour. Whilecontinuing stirring, 107 grams of diluent oil were added, and themixture was stirred for 15 minutes and cooled to room temperature. Theproduct had a sulfur content of 7.50%. The melting point and heat offusion of the polymer, isolated by dialysis, were determined bydifferential scanning calorimetry to be -3.5° C. and 6 J/g,respectively. The number average molecular weight (VPO) of this polymerwas 4,900, and its weight average molecular weight (GPC) was 11,000.

EXAMPLE 5

As an example of the preparation of an alkylated phenol-sulfurcondensate polymer of the present invention, into a four-necked, 1 literround bottom flask, equipped with a mechanical stirrer, a thermometer,addition funnel, nitrogen inlet tube, and a Dean-Stark trap with areflux condenser, were charged 230 grams of hexadecyl phenol produced inaccordance with Example 2, which was heated to 80° C. While stirring, 82grams of a mixture of 76% sulfur dichloride and 24% sulfur monochloridewere added over a period of about one hour, with the temperaturemaintained at about 80° C. After the addition was completed, thereaction mixture was soaked for about five minutes at 80° C. and thenheated to 95° C. and sparged with nitrogen for one hour. Whilecontinuing stirring, 127 grams of diluent oil were added, and themixture was stirred for 15 minutes and cooled to room temperature. Theproduct had a sulfur content of 7.805. The number average molecularweight (VPO) of this polymer was 4,150, and its weight average molecularweight (GPC) was 8,100.

EXAMPLE 6

As an example of the preparation of an alkylated phenol-sulfurcondensate polymer of the present invention, into a four-necked, 1 literround bottom flask, equipped with a mechanical stirrer, a thermometer,addition funnel, nitrogen inlet tube, and a Dean-Stark trap with areflux condenser, were charged 280 grams of heneicosyl phenol producedin accordance with Example 3. The heneicosyl phenol was heated to 80°C. While stirring, 82 grams of a mixture of 76% sulfur dichloride and24% sulfur monochloride were added over a period of about one hour, withthe temperature maintained at about 80° C. After the addition wascompleted, the reaction mixture was soaked for about five minutes at 80°C. and then heated to 95° C. and sparged with nitrogen for one hour.While continuing stirring, 77 grams of diluent oil were added, and themixture was stirred for 15 minutes and cooled to room temperature. Theproduct had a sulfur content of 8,81%. The melting point and heat offusion of the polymer, isolated by dialysis, were determined bydifferential scanning calorimetry to be 19.4° C. and 22 J/g,respectively. The number average molecular weight (VPO) was 5,100, andits weight average molecular weight was 12,000.

COMPARATIVE EXAMPLE 1

The pour point depressancies of the alkyl phenol-sulfur condensatesproduced in Examples 4 to 6 were tested in both light and heavy oils.Pour points for the oils were measured according to ASTM D-97 method,and the results are set forth in Table 1 below, which demonstrates thesignificant pour point depressing properties of these additives.

                                      TABLE 1                                     __________________________________________________________________________                     Pour Point (°F.) (ASTM D 97)                                           Hexadecyl                                                                             Octadecyl                                                                              Heneicosyl                                           Additive                                                                              Phenol-Sulfur                                                                         Phenol-Sulfur                                                                          Phenol-Sulfur                               Run                                                                              Lube  Concentration                                                                         Condensate                                                                            Condensate                                                                             Condensate                                  No.                                                                              Basestock                                                                           (wt. %) (Example 5)                                                                           (Example 4)                                                                            (Example 6)                                 __________________________________________________________________________    1  A     0.00    +15, , +15                                                                            +15, +15 +15, +15                                    2  A     0.05    +15, +15, +15                                                                         -15, -15, -10                                                                          +10, +15, +15                               3  A     0.10    0, +5, +5                                                                             -25, -25, -20                                                                          -5, -5, 0                                   4  A     0.15    -5, 0, +5                                                                             -30, -30, -30                                                                          -10, -10, -10                               5  A     0.20    -5, -5, -5                                                                            -40, -40, -35*                                                                         -15, -15, -10                               6  B     0.00    +20, +20, +20                                                                         +20, +20, +20                                                                          +20, +20, +20                               7  B     0.05    +20, +20, +20                                                                         +15, +20, +20                                                                          +5, +10, +10                                8  B     0.10    +20, + 20, +20                                                                        +10, +15, +15                                                                          0, 0, +5                                    9  B     0.20    +20, +20, +25                                                                         0, +5, +5                                                                              -10, -10, -10                               __________________________________________________________________________     Throughout these examples, Lube Basestocks A and B were as follows:           Lube Basestock A                                                              A Solvent 150 Neutral oil which is a solventrefined hydrocarbon lube          basestock characterized by a viscosity of 150-160 SUS at 100° F.,      viscosity index of 95, and a pour point of about +15° F.               Lube Basestock B                                                              A Solvent 600 Neutral oil which is a solventrefined hydrocarbon lube          basestock characterized by a viscosity of about 600 SUS at 100° F.     a viscosity index of about 95, and a pour point of about +15° F.  

COMPARATIVE EXAMPLE 2

An analysis of the anti-oxidant properties of oils containing theadditive produced in Example 4 was evaluated in accordance with the ERELube Stability Test, DSC Oxidation Stability Test, Diesel Detergency RigTest, and the Panel Coker Test.

The ERE Lubricant Stability Test measures the oxidative stability ofrailroad-diesel and automotive lubricants. In this method, the sample,while stirred and aerated, is held at an elevated temperature for 46hours in the presence of silver and copper-lead specimens that arerepresentative of those in railroad or automotive engines. Thecorrosivity of the oil to the various metals is measured by determiningthe mass loss of the specimens. The stability of the oil is rated beforeand after the oxidation period to obtain the increase in viscosity.

The DSC Oxidation Stability Test is a dynamic measurement of thetemperature at which a lube oil begins to react with oxygen. In thisprocedure, a sample of oil is placed in a differential scanningcalorimeter and heated at 20° C. per minute in a constant flow of air.The temperature at which the oxidative degradation of the oil producesan exotherm is called the onset temperature. The higher the onsettemperature, the greater the thermal stability of the lube oil.

The Diesel Detergency Rig Test evaluates the resistance of a lube oil toform deposits on a hot surface. In this test, the lube oil is pumpedfrom a reservoir to a mixing chamber, where oxygen is injected. Theoil-oxygen mixture is slowly passed through a heated zone leaving asludge and varnish deposit on the inside wall of a glass reaction tube.The amount of deposit on the reaction tube is rated visually for rankingon a demerit scale.

Table 2 includes the results of these tests, and demonstrates that thisadditive significantly improved the oxidation stability of the lube oilin question.

                  TABLE 2                                                         ______________________________________                                        Run            Additive                                                       No.  Test      Conc.    Result                                                ______________________________________                                                                Visc.  Ag      Cu--Pb                                                         Increase                                                                             Corrosion                                                                             Bearing                                                        (%)    (mg)    Loss (mg)                              10   ERE       0        607    +5.1    -129                                        Stability                                                                11   (46 h.)   1.5%      43    +0.8    -115                                                           Onset Temp (°C.)*                              12   DSC       0        242                                                        Oxidation                                                                13   Stability 1.5%     258                                                                           Demerit Rating                                        14   Diesel    0        7.0                                                   15   Detergency                                                                              1.5%     5.0                                                        Rig                                                                      ______________________________________                                         *20° C./min., 40 ml. air/min.                                     

The Panel Coker Test evaluates the thermal degradation and depositformation of oils. It minics the temperature and operating conditions ofa Caterpillar 1-G2 engine. Fully formulated oils are intermittentlysplashed on a preweighed aluminum plate heated to 338° C. The thermalstability and deposit formation properties of the oils are rated interms of weight gained.

An oil formulation containing a dispersant, a detergent, an antiwearagent, a viscosity index improver, and an antioxidant was blended andevaluated in the Panel Coker Test. In Run 1 the antioxidant was acommercial produce, bis (nonyl phenol) sulfide. In Run 2 the antioxidantwas the polymeric octadecyl phenol-sulfur condensate produced inaccordance with Example 4. The results, as shown in Table 3, demonstratethat the polymeric additive of this invention is a superior antioxidant.

                  TABLE 3                                                         ______________________________________                                                             Additive                                                                      Concentration                                                                             Panel Coker                                  Run No. Additive     (wt. %)     Deposits (mg.)                               ______________________________________                                        16      bis (nonyl phenol)                                                                         2.0         70.4                                                 sulfide                                                               17      Example 4    2.0         52.7                                         ______________________________________                                    

Comparative Example 3

The cloud point and pour point depressancies of the alkyl phenol-sulfurcondensates produced in accordance with the present invention weretested in various middle distillate petroleum fuels. Cloud points forthese fuels were measured according to ASTM D 2500 method, and pourpoints for these fuels were measured according to ASTM D97 method. Themiddle distillate fuels used in this example were designated as fuels Athrough C, whose properties were as follows in Table 4:

                  TABLE 4                                                         ______________________________________                                        Diesel Fuel Properties                                                                   Fuel A    Fuel B  Fuel C                                           ______________________________________                                        Cloud Point (°F.)                                                                    +2         +12     +4                                           (ASTM D 2500)                                                                 Pour Point (°F.)                                                                    -15         -10     -5                                           (ASTM D 97)                                                                   API Gravity (*)                                                                            27.1        34.7    34.4                                         (ASTM D 287)                                                                  Distillation (°F.)                                                     (ASTM D86)                                                                    IBP.sup.1    387         318     368                                          10%          437         408     424                                          50%          518         500     507                                          90%          615         615     600                                          FBP.sup.2    660         670     649                                          ______________________________________                                         .sup.1 Initial Boiling Point                                                  .sup.2 Final Boiling Point                                               

The alkyl phenol-sulfur condensates were added to these diesel fuels at0.2 wt. %. The results, set forth in Table 5, demonstrate that tomaximize cloud point reduction an average carbon number of about C₁₈ ismost desired, whole to maximize pour point reduction an average carbonnumber of about C₁₆ is most desired.

                                      TABLE 5                                     __________________________________________________________________________    Effect of Various Alkyd Phenol-Sulfur Condensates                             on the Cloud Points and Pour Points of Diesel Fuels                           Additive           Fuel A  Fuel B  Fuel C                                     Run     Average                                                                             Conc.                                                                              Cloud                                                                             Pour                                                                              Cloud                                                                             Pour                                                                              Cloud                                                                             Pour                                   No.                                                                              Example                                                                            Carbon No.                                                                          (Wt. %)                                                                            Point                                                                             Point                                                                             Point                                                                             Point                                                                             Point                                                                             Point                                  __________________________________________________________________________    18 5    16    0.0  +2  -15 +12 -10 +4  -5                                     19 5    16    0.2   0   -45*                                                                             +10  -45*                                                                             +4  -40*                                   20 4    18    0.0  +2  -15 +12 -10 +4  -5                                     21 4    18    0.2   -6*                                                                              -20  +6*                                                                              -35  -4*                                                                              -25                                    22 6    21    0.0  +2  -15 +12 -10 +4  -5                                     23 6    21    0.2  -4  -15  +8 -10 N/P.sup.1                                                                         N/P.sup.1                              __________________________________________________________________________     .sup.1 Not performed                                                     

Although the invention herein has been described with reference toparticular embodiments, it is to be understood that these embodimentsare merely illustrative of the principles and applications of thepresent invention. It is therefore to be understood that numerousmodifications may be made to the illustrative embodiments and that otherarrangements may be devised without departing form the spirit and scopeof the present invention as defined by the appended claims.

We claim:
 1. A polymer composition capable of improving the lowtemperature flow properties and oxidation stability of hydrocarbon oilcomprising the condensation reaction product of reactants comprisingalkylated phenol, comprising at least 80 mole percent difunctionalalkylated phenol, and sulfurizing agent wherein:(a) said polymercomposition has a number average molecular weight of at least about3,000 and a molecular weight distribution of at least about 1.5; (b) insaid alkylated phenol reactant the alkyl groups: (i) are essentiallylinear; (ii) have between 6 and 50 carbon atoms; and (iii) have anaverage number of carbon atoms between about 12 and 26; (c) not morethan about 10 mole percent of the alkyl groups on said alkylated phenolhave less than 12 carbon atoms and not more than about 10 mole percentof the alkyl groups on said alkylated phenol have more than 26 carbonatoms.
 2. The polymer composition of claim 1 wherein said sulfurizingagent is selected from the group consisting of elemental sulfur andsulfur-containing compounds having the formula S_(x) Cl₂, wherein x is anumber from 1 to
 2. 3. The polymer composition of claim 1 wherein saidessentially linear alkyl groups comprise at least 40 mole percent alphamethyl substituted linear alkyl groups.
 4. The polymer composition ofclaim 1 wherein said essentially linear alkyl groups comprise at least50 mole percent alpha methyl substituted linear alkyl groups.
 5. Thepolymer composition of claim 1 wherein said average carbon number ofsaid alkyl groups of said alkylated phenol is between about 14 and 24.6. The polymer composition of claim 5 wherein said average carbon numberof said alkyl groups of said alkylated phenol is between about 16 and22.
 7. The polymer composition of claim 1 wherein said average carbonnumber of said alkyl groups of said alkylated phenol is between about 18and
 20. 8. The polymer composition of claim 1 wherein said averagecarbon number of said alkyl groups of said alkylated phenol is betweenabout 16 and
 19. 9. The polymer composition of claim 1 wherein saidaverage carbon number of said alkyl groups of said alkylated phenol isbetween about 17 and
 21. 10. The polymer composition of claim 1 whereinsaid molecular weight distribution is from about 1.5 to about
 34. 11.The polymer composition of claim 1 wherein said number average molecularweight is at least about 4,000.
 12. The polymer composition of claim 1wherein said number average molecular weight is from about 3,000 toabout 60,000.
 13. The polymer composition of claim 1 wherein saidpolymer forming reactants include at least one comonomer selected fromthe group consisting of: ##STR13## wherein R₆, R₇ and R₈ are eachindependently selected from the group consisting of hydrogen, alkyl,aryl, alkoxy, aryloxy, alkyl mercapto, and halogen.
 14. The polymercomposition of claim 13 wherein said comonomer is present in an amountof less than about 10 wt. % of said polymer.
 15. The polymer compositionof claim 13 wherein said comonomer of formula (II) comprises phenol andsaid comonomer of formula (III) comprises bisphenol A.
 16. A fuel oilcomposition comprising a major amount of a fuel oil and a lowtemperature flow and oxidation stability improving amount of a polymericadditive comprising the condensation reaction product of reactantscomprising alkylated phenol, comprising at least 80 mole percentdifunctional alkylated phenol, and sulfurizing agent wherein:(a) saidpolymer has a number average molecular weight of at least about 4,000and a molecular weight distribution of at least about 1.5; (b) in saidalkylated phenol reactant the alkyl groups: (i) are essentially linear;(ii) have between 6 and 50 carbon atoms; and (iii) have an averagenumber of carbon atoms between about 12 and 26; (c) not more than about10 mole percent of the alkyl groups on said alkylated phenol have lessthan 12 carbon atoms and not more than about 10 mole percent of thealkyl groups on said alkylated phenol have more than 26 carbon atoms.17. The fuel oil composition of claim 16 comprising between about 0.005and 10 wt. % of said additive.
 18. The fuel oil composition of claim 16comprising between about 0.01 and 2 wt. % of said additive.
 19. The fueloil composition of claim 16 wherein said essentially linear alkyl groupscomprise at least 40 mole percent alpha methyl substituted alkyl groups.20. The fuel oil composition of claim 16 wherein said polymer includesbetween about 5 and 20 wt. % sulfur.
 21. The fuel oil composition ofclaim 16 wherein said reactants further comprise comonomer representedby the formula ##STR14## wherein R₆ and R₇ are selected from the groupconsisting of hydrogen, alkyl, aryl, alkoxy, aryloxy, alkyl mercapto,and halogen.
 22. The fuel oil composition of claim 16 wherein saidpolymer-forming reactants further comprise comonomer represented by theformula: ##STR15## wherein R₈ is independently selected from the groupconsisting of hydrogen, alkyl, aryl, alkoxy, aryloxy, alkyl mercapto,and halogen.
 23. The fuel oil composition of claim 16 wherein saidessentially linear alkyl groups comprise at least 50 mole percent alphamethyl substituted linear alkyl groups.
 24. The fuel oil composition ofclaim 16 wherein said average carbon number of said alkyl groups of saidalkylated phenol is between about 14 and
 24. 25. The fuel oilcomposition of claim 16 wherein said average carbon number of said alkylgroup of said alkylated phenol is between about 16 and
 22. 26. The fueloil composition of claim 16 wherein said average carbon number of saidalkyl groups of said alkylated phenol is between about 18 and
 20. 27.The fuel oil composition of claim 16 wherein said average carbon numberof said alkyl groups of said alkylated phenol is between about 16 and19.
 28. The fuel oil composition of claim 16 wherein said average carbonnumber of said alkyl groups of said alkylated phenol is between about 17and
 21. 29. The fuel oil composition of claim 16 wherein said molecularweight distribution is from about 1.5 to about
 34. 30. The fuel oilcomposition of claim 16 wherein said number average molecular weight isfrom about 4,000 to about 60,000.
 31. A method for producing a polymericadditive suitable for improving the low temperature flow properties andoxidative stability of hydrocarbon oil which comprises (1) providingalkylated phenol, comprising at least 80 mole percent difunctionalalkylated phenol, derived from the reaction of (a) phenol and (b) linearalpha-olefin having (i) from 6 to 50 carbon atoms, (ii) an averagecarbon number of form about 12 to 26; and (iii) not more than about 10mole percent containing less than 12 carbon atoms and not more thanabout 10 mole percent containing more than 26 carbon atoms, saidalkylation being conducted at a temperature of from about 50° to about200° C. in a manner and under conditions sufficient to render the alkylgroups of said alkylated phenol essentially linear; and (2) condensingalkylated phenol consisting essentially of alkylated phenol provide dinaccordance with step (1) with a sulfurizing agent so as to producesulfur bridged condensate of said alkylated phenol and said sulfurizingagent having a number average molecular weight of at least about 3,000and molecular weight distribution of at least about 1.5.
 32. The methodof claim 31 wherein said sulfurizing agent is selected from the groupconsisting of elemental sulfur and sulfur-containing compounds havingthe formula S_(x) Cl₂, wherein x is an integer from 1 to
 2. 33. Themethod of claim 31 wherein said condensing step is conducted in thefurther presence of at least one comonomer represented by the formulaselected from the group consisting of; ##STR16## wherein R₆, R₇ and R₈are each independently selected from the group consisting of hydrogen,alkyl, aryl, alkoxy, aryloxy, alkyl mercapto, and halogen, and whereinsaid comonomer is present in an amount of less than about 10 wt. % ofsaid combination of said alkylated phenol and said surfurizing agent.34. The method of clam 31 wherein said linear alpha-olefin comprises amixture of linear alpha-olefins.
 35. The method of claim 31 wherein saidalkylation is conducted in the presence of an acidic crystallinealuminasilicate zeolite catalyst in order to minimize the production ofdialkylate therein.
 36. The method of claim 35 wherein said zeolitecatalyst has a silica to alumina molar ratio of from about 3:1 to about6:1.
 37. The method of claim 35 wherein said zeolite catalyst has asurface area of at least about 625 m² /g.
 38. The method of claim 35wherein said zeolite catalyst has a free pore diameter of between about6 A and about 8A.
 39. The method of claim 35 wherein said alkylation isconducted using a molar ratio of said phenol to said linear alpha-olefinof less than about 2:1.
 40. The method of claim 39 wherein saidalkylation is conducted using a molar ratio of said phenol to saidlinear alpha-olefin of between about 1.7:1 and about 1:1.
 41. Polymericadditive for improving the low temperature flow properties and oxidativestability of hydrocarbon oils prepared by the process of reacting (a)alkylated phenol represented by the formula: ##STR17## wherein Rrepresents essentially linear alkyl having from 6 to 50 carbon atoms inwhich the average number of such carbon atoms in all of the groupsconstituting R is between about 16 and 22, wherein not more than about10 mole percent of said alkyl groups have less than 16 carbon atoms andnot more than about 10 mole percent of said alkyl groups have more than22 carbon atoms, with (b) sulfurizing agent selected from the groupconsisting of elemental sulfur and sulfur-containing compounds havingthe formula S_(x) Cl₂, wherein x is an integer from 1 to 2, andoptionally (c) comonomer selected from the group consisting oftrifunctional monomers represented by the formula: ##STR18## andtetrafunctional monomers represented by the formula: ##STR19## whereinR₆, R₇, and R₈ are selected from the group consisting of hydrogen,alkyl, aryl, alkoxy, aryloxy, alkyl mercapto, and halogen, to formpolymer condensate having a number average molecular weight of at leastabout 5,000 and a molecular weight distribution of at least 1.5.
 42. Theadditive of claim 41 wherein said essentially linear alkyl groupscomprise at least 40 mole percent alpha methyl substituted linear alkylgroups.
 43. The additive of claim 41 wherein R has an average number ofcarbon atoms between about 18 and
 20. 44. The additive of claim 41wherein R₆, R₇ and R₈ are hydrogen.
 45. The additive of claim 41 whereinR₈ is selected from the group consisting of hydrogen and methyl.